Supersensitization of photographic emulsions with complex merocyanine dyes



Patented Apr. 21, 1953 SUPERSENSITIZATION OF PHOTOGRAPHIEl EMULSIONS WITH COMPLEX MEROCYA- NINE DYES Burt H. Carroll, Rochester.,A N: Y., assigner to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application March 1, 1952 Serial'No. 274,445

Claims.

This invention relates to photographic emulsions comprising certain4 diaryloxythiacarbocyanine dyes, and as supersensitizers therefor, certain complexk merocyanine dyes.

It is knownA in the art of making photographic emulsionsthat certain dyes of the` cyanine class Ialter the sensitivity` of photographic emulsions .of the gelatino-silver kind, when the` dyes are incorporated in the emulsions; It is also known `that. the sensitization` produced by a given dye varies somewhat; with the type of emulsion in which` the dye is` incorporated. Furthermore, the sensitization of al given emulsion by a given dyemay be altered by varying conditions in the emulsion. For example, the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration (i. e. increasing the alkalinity)A or both. Thus, sensitization can be increased by bathing plates,l coated with a spectrally sensitized emulsion, in water or in aqueous solutions of ammonia.. Such a process of altering the sensitivity of a sensitizedV emulsion by increasing `the silver `ion concentration and/or by decreasing the hydrogen ion concentration is commonly called hypersensitization Hypersensitized emulsions have generally poor keeping qualities.

I have now found a new means of altering the sensitivity in emulsions containing certaindiaryloxythiacarbocyanine dyes of a particular type. Since, the conditions in the emulsion, i. e. the .hydrogen ion and/or the silver ion concentration undergo. little or no change in my new` method, I. shall designate my new method as a kind of supersensitizatiom Itis, therefore, an; object of my invention to provide photographic emulsions comprising certain, diaryloxythiacarbocyanine dyes and; as supersensitizers therefor, certain complex merocyanine` dyes.. Another object is to provide a process. for preparing these supersensitized emulsions. Other objeots will become apparent from a4 consideration of the following description and examples.

The` complex merocyanine dyes useful in `practicing my inventionA have been previouslyl proposedas sensitizers` for photographic emulsions in Brooker U.` S. Patent 2,544,629,1ssued November,23,` 19.48, beginning at line 62, col. 17. The `parent merocyanine` dyes. from which` the complex` dyes are, derivedV have no corresponding supersenstizing eil'ects. Nor do the complex cyannes Lalso described in 2.454.629) derived from the samepareut nierocyanin `dyes exhibit the. supersensitizina effects shown in the.`v instant Apracticing my invention, CDmprise the 3,3di

methyl- 8,10.- diaryloxythiacarbocyanine dyes of Brooker andWhite U. S. Patent 2,478,366, issued August 9, 1949.` These dyes share the characteristic of a sharp maximum, lying ata wavelength considerably longer than that of the dye in the molecular state. Further, these dyes have unusually strong andi sharp `maxima of absorption and sensitivity, but when used alone, their usefulness is limited by low speeds, which may be traced to low efficiency of energy transfer from, the dye to, the silver halideY grain, and to desensitization. (Spence and Carroll, Jouix Phys. 8a` Coll. Chem., vol. 52` (1943.) D.. 1.0190)4 'Ijhe 3,3'diethyl8,10-diaryloxythiacarbocyanine dyes,

`3,3' diethyl 8,10 daryloxyselenacarbocyanine dyes, and 3,3 diethyl 8,10, diaryloxyoxacarbocyanine dyes have not given consistent` results which would justify their use for the purposes of this invention.

. The 3,3 dimethyl -8,10y diaryloxythiacarbocyanine dyes useful in practicing my invention can advantageously be represented4 by the4 following general. formula.:

wherein R and R1 each represents an aryl group, such asv phenyl, o, m-, and p-tolyl, o-, m, and p-methoxyphenyl, o-, m, and p-chlorophenyl, -naphthyl, etc. (e. g. especially a mononuclear aromaticnucleus ofv the benzene series), Z and Zr each represents the nonmetallic atoms necessaryV to complete a heterocyclic nucleus of the benzothiazole series and lili4 represents an anion, such as bromide, iodide, chloride, perchlorate, thiocyanate, methylsulfate, ethylsulfate, benzenesulfonate, p-toluenesulfonate, etc. The dyes represented by Formula I can be prepared ac.- cording to the method4 described in U. S. Patent 2,478,366 mentionedabove.

The complex. merecyanne useful in practicing my invention can be represented by the following general formula:

o=c-NRa -N-R. R2I\T(-L =L)dii:`0 (=L,L),,i.=, l:Si \S/ est sensitivity).

wherein R2, R3, and R4 each represents an alkyl group, such as methyl, ethyl, n-propyl, n-butyl, n-heptyl, -hydroxyethyl, -carbethoxymethyl, -methoxyethyl, ethoXyethyl, hydroxy-- ethoXy--ethoxyethyl, ete., L represents a methine group (i. e. -CR=, wherein R' is a hydrogen atom, an alkyl group (methyl, ethyl, etc.) or an aryl group (phenyl, tolyl, etc.) etc.) d and n eachV The complex merocyanine dyes selected from those represented by Formula I I above are advantageously employed at concentrations on the order of 0.001 to 0.05 g. per mole of silver halide in the emulsion.

Generally speaking, the ratio of concentration of the complex merocyanine dye (Formula II) to diaryloxycarbocyanine dye (Formula I) can vary represents a positive integer of from l to 2, and Z2 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from those of the benzothiaole series, the a-naphthothiazole series, the -naphthothiazole series, the benzoxazole series, and the quinoline series. 'I'he complex mercyanine dyes represented by Formula II above can be prepared according to the method described in U. S. Patent 2,454,629, mentioned above.

According to my invention, I incorporate one or more of `the diaryloxycarbocyanine dyes se.- Vlected from those represented by Formula I above with one or more oi the complex merocyanine dyes selected from those represented by Formula II above in a photographic emulsion. My invention is particularly directed to the ordinarily employed gelatino-silver-halide emulsions. However, my supersensitizing combination can be employed in silver halide emulsions in which the centration of the dye in the emulsion, but rather passes through a maximum as the concentration is increased. In practicing my invention, the individual sensitizing dyes are advantageously employed in a concentration somewhat less than their optimum concentration (i. e. the concentration at which the individual dyes` give great- If each of the dyes in the supersensitizing combination is employedin itsoptimum concentration, it is possible, in certain cases 'that the sensitization produced by the supersensitizing combination Will have passed through a maximum. i

The optimum concentration of an individual sensitizing dye can be determined in a manner well known to those skilled in the art by measuring the sensitivity of a series of test portions of the same emulsion, each portion containing a different concentration of the sensitizing dye. The optimum concentration of my supersensitizing combinations can, of course, be readily determined in the same manner, by measuring the sensitivity of a series of test portions of the same emulsion, each portion containing diierent concentrations of the individual dyes in the combination. In determining the optimum concentration for the supersensitizing combination, it is advantageous to employ, at rst, concentrations of the individual dyes less than their optimum concentrations. The concentrations of the individual dyes can then be increased until the optimum concentration of the supersensitizing combination is determined. Y

Ordinarily the optimum or near optimum concentration of the diaryloxycarbocyanine dyes, selected from those represented by Formula I above which I employ in practicing my invention, is of the order of from 0.02 to 0.20 g. per mole of silver halide in the emulsion.

rather widely in my new combinations, e. g. from 1:100 to 1:2 (by weight) in many cases.

The methods of incorporating sensitizing dyes in emulsions are well known to those skilled in the art. In practicing my invention, the sensitizing dyes can be incorporated in the emulsions separately or together. It is convenient to add the dyes separately in the form of solutions in appropriate solvents. Methanol and ethanol, especially the former, have proven satisfactory as solvents for the dyes of Formula I which I employ, while acetone has proven satisfactory as a solvent (with small amounts of o-chlorophenol to improve solubility in some instances) for the complex merocyanine dyes oi' Formula II. The dyes are advantageously incorporated in the finished, washed emulsions and should be uniformly distributed throughout the emulsions. The following procedure is satisfactory: Stock solutions of the sensitizing dyes desired are prepared by dissolving the dyes in appropriate solvents as described above. Then, to one liter of a owable gelatino silver halide emulsion, the desired amounts of the stock solution of one of the dyes is slowly added, while stirring the emulsion. Stirring is continued until the dye is thoroughly incorporated in the emulsion. Then the desired amount of the stock solution of the second dye is slowly added to the emulsion, while stirring. Stirring is continued until the second dye is thoroughly incorporated. The supersensitized emulsion can then be coated out on a suitable support, such as glass, cellulose derivative lm, resin lm, or paper, to a suitable thickness and allowed to dry. The details of such coating methods are well known to those skilled in the art.

The amounts of the individual sensitizing dyes actually incorporated in the emulsion will vary somewhat from dye to dye, according to the emulsion employedV and according to the effect desired. The regulation and adoption of the most economical and useful proportions will be apparent to those skilled in the art upon making the ordinary observations and tests customarily employed in the art. Accordingly, the foregoing procedures and proportions are to be regarded only as illustrative. Clearly my invention is directed to any emulsion containing a combination of the aforesaid sensitizing dyes whereby a supersensitizing effect is obtained.

The following examples Will serve to illustrate further the manner of practicing my invention. To diierent portions of the same batch of photographic gelatino-silver bromiodide emulsion were added (l) a diaryloxycarbocyanine dye selected from those of Formula I above and (2) a combination of the diaryloxycarbocyanine dye and a complex merocyanine dye selected from those represented by Formula II above. In some instances a third coating was prepared using the same emulsion formula and adding only one of the complex merocyanine dyes selected from those of Formula II. In general, the table will show that this third coating gave onlya low speed or one too small to measure (designated in the table). Diierent emulsions Were used lin someiof the examples, although the emulsions of "each individual example 'are obtained from the )in `the usual :manner .in a spectrograph and a sensitometer (type 1b) through a Wratten 25 filter, i, e. a lter which transmits substantially no light of Wavelength shorter than 580 ma. Followingare several examples of .such emulsions together with the speed (red) ,gamma and fog obtained.

:L6 `the sensitivity conferred onthe emulsion by the complex merocyanine dye alone is shown, since the sensitivity conferred bythe complex merocyanine in question is too Weakto besigniiicant in the comparisons shown.

In Fig. 1, curve A `represents the sensitivity of an ordinary gela-tino-silver-bromiodde emulsion sensitized with `8,10-di(p-chlorophenoxy)-3.3 dimethyl thioearbocyanine` p-toluenesulfonate, and curve B represents thesensitivity oi' thesame emulsion containing 8,10-di(p-chlorophenoxy) 3,3 "dimethylthiacarbocyanine p-toluenesulfonate and 5- i (Methyl-2(1) --naphthothiazolyldene) a -ethylethylidenel-3methoxyethy1-2 (3 -f -methoxyethyl-4-oxo-2-.thioro-5-thiazolidylidene) -4-thiazolidone. I'hesensitome'tricmeasurements for these emulsions are given in VEx ample `5 of the above table.

1n Fig. 2, curve C represents the sensitivity of an ordinary gelatinesilver-bromodide emulsion sensitized with 3,3dimethyl8,l0di(mto1oxy).

Example Dye (g.` per; mole of silver halide in emulsion) IRed` Light Exposure l Speed!) .Gemma Fog (a) (0.080) (e) SJC-di(pmethoxyphenoxy)3,3 --dl (f) dye (a) (0.001) with dye (c) (.080) (r1) dye (fz) (0.040) with dye (e) (.080)

(12) dye (o) (0.001) with dye (m) (0.080) (Il) 3-ethyl-5-(1-ethy1-2(1)quinolylideue (T) dye (m) (0.080) With dy (II) 001) thazolidone (0.001)

(m) dye (Z) (0.001) with dye (u) (0.080)

done (0.001) (0() dye (p') (0.001) with dyem) (0.080)

ethyl-fi-oxoLZ-thionoehiazolidylidene)enthiazolidone (0.

D C OO C OO OO D'O l[(a) dye ((2) (0.001) with dye (u) (0.080) (h) ,5-[(1-et11y12(l)-Snaphthothiazolyliden thiono-ftliiazolidylidene)-4thiazolidone (0. (c) dye (b) (0.001) with dye (fu) (0.080) (d) 2-(3-carbethoxymethyJ-i-oxo `znlylidene)ethylidene]-llthiazolidone (0. (el) dye (df) (0.001.) with dyed.) (0.080)- [(f.) 2-(3-carbethoxymethyl-Li-oxo-Z-thiono `ethylidene]4thiaz0ldone (0.001) 10') dye 0040.001) with dye 00 0050) {(h) 3-ethyl-5I(3ethyl2(3)-b enzothiazoly dylidene).4thiazolidone (0.001) 10") eye-01') (0.001) with dy@ 0) y(0:0540) {(j) 3-ethy1-5;[(3ethyl2(3)-benzothiazolyhden The accompanying drawing illustrates the supersensitizing eiect obtained with three of my new combinations in silver bromiodide emulsions. Each gure of the drawing is a diagrammatic reproduction of two spectrograms. In each figure the sensitivity of the emulsion containing the daryloxyearbocyanine dye is represented by Vthe lower curve. The upper curve .represents the sensitivity conferred .on the .emulsion by the .com- .bination `of the Vdiaryloxycarbocyanine dye .and vthe complex merocyanine dye. "Nocurve-showing obtained using gelatino-silver-bromiodide emulsions, excellent results have also been obtained using gelatino-silver-chlorobromide emulsions. Emulsions which form the latent image mostly inside the silver halide grains, such as the emulsion set forth in U. S. Patent 2,456,956, dated December 21, 1948, can also be employed in practicing my invention.

The emulsions prepared in accordance with my invention can be coated in the usual manner on any suitable support, e. g. glass, cellulose nitrate film, cellulose acetate film, polyvinyl acetal resin l nlm, paper or metal.

The following examples will serve to illustrate the manner whereby the complex merocyanine dyes used in my invention can be prepared.

- x S\ oc-Nomcmoom v A mixture of 2.28 g. (1 mol.) of 5-[(1ethyl 2(1) naphthothiazolylidene) a-ethylethylidene]-3--methoxyethylrhodanine and 0.93 g. (1

v mol.) of methyl p-toluenesulfonate Were fused together over a free name and then heating was continued for 4 hours at the temperature of the steam bath. The crude addition product, thus triethylamine in 25 ml. of dry pyridine were heated together at the refluxing temperature for 5 minutes. After cooling, the dye was collected on a lter and washed with methyl alcohol. The yield of dye was 86% crude and 72% after two recrystallizations from pyridine. The green crystals had melting point 272-273 C. with decomposition.

The 5 [(1 ethyl 2(1) --naphthothiazolylidene) -a-ethylethylidenel- 3 methoxyethylrhodanine used above was prepared as follows:

A mixture of 4.50 g. (1 mol.) of 1-ethyl-2-thio- .rhodanine and 0.53 g. (1 mol. plus 5% excess) of f 2.79 g'. (l mol.)'of methyl-p-toluenesulfonate was fused over a free iiame and then heating was continued at the temperature of the steam bath for 4 hours. This crude addition product, 2.87 g. (1 mol.) of --methoxyethylrhodanine and 1.60 g. (1 mol. plus 5% excess) of triethylamine in 50 ml. of absolute ethyl alcohol were heated together at the reiiuxing temperature for 30 minutes. After cooling, the dye was collected on the lter and Washed with methyl alcohol. The crude dye was dissolved in hot pyridine and precipitated from the pyridine ltrate by the addition of methyl alcohol. After another such purification the yield of dye was 78%. The

vpurplish crystals had melting point 184185 C.

with decomposition.

The 3-/3-methoxyethylrhodanine used above Vwas prepared as follows:

A mixture of 50 g. (1 mol.) of 85% potassium hydroxide dissolved in 300 ml. of Water and 77 g. (l mol.) of a 72% aqueous solution of -methoxyethylamine was stirred mechanically as 57 g. (1 mol.) of carbon disulfide was added, ovei` a period of 30'm'inutes. The reaction mixture was heated, with stirring, on the steam bath for about 2 hours. After dissolving 72 g. (1 mol.) of chloroacetic acid in ml. of water the solution was neutralized with sodium carbonate and the resulting solution was added to the reaction mixture. The mixture was stirred for about one hour, stood overnight at room temperature and then made acid to Congo red paper with'dilute sulfuri-c acid. About two hours later theV oily layer was collected at the separatory funnel. The aqueous layer was extracted with benzene. The combined benzene extract and the oily layer was O C- NCHZCHzO CH3 l OC--NCHCHsOCHa CH-CHLC C A mixture of 2.14 g. (1 mol.) of 5-[(1ethyl 2( 1) naphthothiazolylidene) ethylidene] 3 -methoxyethylrhodanine and 3.8 g. (1 m'ol. plus 300% excess) of methyl-p-toluenesulfonate was heated for 4 minutes at 160 C.V The crude addition product, thus formed, and 1.2 g. (1 mol.) of 3--methoxyethylrhodanine in 25 ml. of dry pyridine were heated together to the boiling point, then 0.5 g. (1 mol.) of triethylamine was added and the reaction mixture was heated at the refluxing temperature for 30 minutes. After chilling, the dye was collected on a lter and washed .prgpionylmethylene naphthothiazoline and 75 ,with methyl alcohol.r The yield of dye was 75% 2,63515981 9 1C)1 crudeand 38%' after tworecrystallizations from' rhodanine and 1.01 g. (1 mol.) of triethylamine pyridine. The green crystals had melting point in 250ml. of absolute ethyl alcohol was heated 292-295" C. with decomposition. at the refiuxing tempera-ture for 50 minutes. 'Ihef5` [(1 ethyl 2(1) naphthothia- After chilling, the solids Were collected on the zolylidene) ethylidene] 3 methoxyethylrho.` 5 `ilterand washed. withmethyl alcohol. The resieV danine used in the above example Was prepared due wastransferred toa beaker.. stirred with hot as follows: methyl alcohol and the-- suspension was` ltered A mixture of 27.2 g. (1 mol.) of 2 acetanilihot. The yield of reddish crystals after one redovinyl naphthothiazole ethoptoluenesul crystallization Was 25%.

alcohol. The remaining residue Was stirred with l5 500.1111. of hot methyl alcohol and the suspension A mixture` `of 1.68 g. (1 mol.) of 5[(1e thy1f was ltered hot. After another such treatment 2( 1), naphthothiazolylidene) a phenyl-` withhot methyl: alcohollthe `yield of dye was 61% ethylidenel. 3 methoxyethylrhodanine and and. the green crystals had melting .point 2.39- 1-24 g- (1 m01. plus 100% excess) of methyl P- 241 C. with decomposition. toluenesulfonate` was fused over a, free 11eme for Example 3; 5 E (3 hydmyemyz. 2(3) 3o a few minutes. The. Crude addition.productthus` naphzhmiazozyzifzene)emyzifzenei 3- fom-16d: DJG-4 g (l nml-)- Of Smet'hoxyethylf' memoyethyz 2 3 methoyethyz 4 rhodanineand g. (1 mol.,plus 5%` excess) of wou-done ed together atthe refluxng temperature for '7` S\ o'cr-iionzcmoora oc--zlxrcmomocm C=CHCH= Cm CS (S/l \S/ r onzcHzoH A mixture of 1.11 g. (1 mol.) of .l5-[(3--hyminutes. The cool reaction mixture was stirred droxyethyl 2(3) a naphthothiazolylidene) with ether. After chilling, the dye was collected ethylidenel-Seemethoxyethylrhodanineand) 0.93 0na lter and washed with methyl alcohol. The' g (1 m01, plus 100% excess) of methyl p-tolu- 50 dye Wasdissolvedin boiling" pyridine; and precipienesulfonate was heated together at the temperatated by` adding methyl alcoholto the, {11i-,eredturefof` the steam bath for 6 hours. The crude pyridine-solution. The yieldof dye-after another' addition product, 0.46g. (1 mol.) of Sept-methoxysuch purificationiwas 52%. Thedark green crysethylrhodaniiie,` and 0.25 gi (1 mol.) of triethylatalshad melting point 311 C. with decomposition. mines in 251ml. of dry pyridine were heated to- The 5 [(11 ethyl -i 2(1) naphthothgether` at the reiluxing temperature for 5 min-` azolylidene).-a-phenylethylidene] .3 methtites.` The cool reaction mixture was stirred with` oxyethylrhodaninei usedl in the above example sorneimethyl alcohol and the` Whole was chilled. Wasprepared as follows:

The scglid was collected on a.lter and washed A mixture of 10.41 g. (1 mol.) of 1etliy1 2..l

with methyl, alcohol. The residue was stirred thobenzoylemethylene-enaphthothiazoline and with 300 ml. of boiling methyl alcohol and the` 5.58 g. (l mol.) of methyl` p-tolueriesulfonateA suspension was filtered hot. After another such Was heatedl over a free `flame. The crude addi treatment, the dye was dissolved in` boiling pyrition. product., 5.73 g. (ll mol.) of- 3-- methoxwdine` and precipitated by adding.A methyl alcohol ethylrhodanine and 3.18-` gl, (11 m01 plus 5% eX- to the ltered pyridine solution. The. yield of. cess) of triethylamine in 100` ml. of absolute dyeafteramthersmh purification Wa.; 33 The` ethyl alcoholwerefheated; togetherrat the refluxdark green crystals had melting point 299-301" ing temperaturefor 40 minutes. After chilling; i

C. with decomposition. the reaction mixture` Wasistirredl with ether;` the The 5.- [(3 hydroxyethyl 2(3)` a naphsuspension; was` ltered andY the` residue was; thothiazolylidene)ethylidenel 3 methoxy- 70 Washedwith ether. Thelcrudeidyewas dissolvedl ethylrhodanine used in the above example was in hot pyridine` and precipitated from the pyrif prepared as follows:

A mixture of 4.27 g. (1 mol.) of Z--anilinc` After two further purifications the yield of dye dine filtrate by the addition of ethyl` alcoholi. l

vinyl. e naphthothazole hydroxyetho.` was 22%.` The green crystals had melting point bromide, 1.91 g. (1 mol.) of 3---me'hoxyethyl-` 75 242-2-13' C; with decomposition.

Example 25.--3-ethyZ-5-[(3-ethyZ-2(3) -beneoy wherein R' and R1 each represents an aryl group, 1

Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and X represents an vA mixture of 1.9 g. (1 mol.) of 3-ethyl-5-[C3- ethyl- 2 (3) benzothiazolylidene) aethylethylidenelrhodanine and 1.9 g. (1 mol. plus 100% excess) of methyl p-toluenesulfonate were heated together for one hour in an oil bath at 140l50 C. The cake of crystals was crushed raider acetone and the suspension was filtered. The crude addition product, thus obtained, 1.33 g. (l mol.) of crude 3-(-hydroxy--ethoxy-- ethoxyethyl)rhodanine and 0.5 g. (l mol.) of triethylamine in 25 ml. of absolute ethyl alcohol were heated together at the reuxing temperature for minutes. After chilling, the dye was Washed on the lter with methyl alcohol. The yield of dye was 60% crude and '7% after two recrystallizations from acetone. The dark green crystals had melting point 180-183 C. with decomposition.

The 3- (-hydroxy--ethoxy--ethoxyethyl) rhodanine used in the above example was prepared in the same manner as the B--methoxyethylrhodanine of Example 2l above, except that -hydroXy--ethoxy--ethoxyethylamine was used instead of -methoxyethylamine. Although the oily layer of the S-(-hydroxy--ethoxy-- ethoxyethyDrhodanine was insoluble in benzene, a mixture of the two was heated on the steam bath, under reduced pressure, rst to dry the oily layer and then to remove the benzene. The residue of 8.8 g. of pale yellow oil was used without further purication.

The 3-ethyl-5-l (3-ethyl-2 3) -benzothiazolylidene)-a-ethylethylidenelrhodanine used in Example 25 was prepared as follows:

A mixture of 44.4 g. (l mol.) oi' 3-ethyl-2-thiopropionylmethylenebenzothiazoline and 66.0 g. (1 mol. plus 100% excess) of methyl p-toluenesulfonate was heated at the temperature of the steam bath for 2 hours. The crude reaction mixture was washed with absolute ether. The addition product, 28.8 g. (1 mol.) of 3-ethylrhodanine and 17.9 g. (1 mol.) of triethylamine in 400 ml. of absolute ethyl alcohol were heated together at the refluxing temperature for 30 minutes. After chilling, the dye was collected on a filter and washed with methyl alcohol. A second portion of dye was isolated from the ltrate by treating it with water. The yield of dye, thus obtained, was 35% The above examples are merely representative of the methods which can be used to prepare the complex merocyanine dyes useful in practicing my invention, it being understood that other dyes represented by Formula II can be prepared in like manner.

What I claim as my invention and desire secured by Letters Patent of the United States is:

-1. A photographic silver halide emulsion sensitized with a supersenstizing combination of at least one diaryloxythiacarbocyanine dye selected from those represented by the following general formula:

anion, and at least one complex merocyanine dye selected from those represented by the following general formula:

wherein R2, R3, and R4 each represents an alkyl g-roup, L represents a methine group, d and n each represents a positive integer of from 1 to 2, and Z2 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those of the a-naphthothiazole series, those of the -naphthothiazole series, those of the benzoxazole series, and those of the quinoline series.

2. A photographic gelatine-silver halide developing-out emulsion sensitized withv a supersensitizing combination of at least one diaryloxythiacarbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an aryl group, Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and X represents an anion, and at least one complex merocyanine dye selected from those represented by the following general formula:

wherein Rz, Rs, and R4 each represents an alkyl group, L represents a methine group, d and n each represents a positive integer of from 1 to 2, and Z2 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those of the a-naphthothiazole series, those of the -naphthothiazole series, those of the benzoxazole series, and those of the quinoline series.

3. A photographic gelatino-silver-bromiodide developing-out emulsion sensitized with a supersensitizing combination of at least one diaryloxythiacarbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an aryl group. Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and X represents an anion. and at least one complex merocyanine dye spencer selected from thoserepresented by the following general formula:

wherein-R and R1 eachrepresents-a mononuclear aromatic group of the benzene series, Z andA Z1 each represents the nonmetallic` atoms necessary to complete a` heterccyclic` nucleus of the benzothiazcle series, and X represents an anion, and at leastone complex merccyanine dye selected from those represented'` by.' thetfollowing general formula:

wherein `R2 represents a member selected from thegrcup consisting: of a. methyl group, anethyl group, and a'. -hydroxyethyl group, Re and R4 each represents axmexnber` selected fromthe group consisting of a methyl group,` an ethyl group, a n-heptyl group, a rrnethoxyethyl group, a carbethoxymethyl group and` a: -hydroxy--ethoxy- -ethoxy-ethyl group, L represents a. methine group, d andn each represents a positive integer of from l to 2, and Zarepresents theA nonmetallic atoms` necessary to complete a: heterocyclic nucleus selected from the group consisting of those of the benzothiazole series, those of the a-naphthothiazole series, those of the -naphthothazole series, those of the benzoxazole series, and those of the quinoline series.

5. A photographic silver halide developing-out emulsion sensitized with a supersensitizing cornbination of at least one diaryloxythiacarbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents a mononuclear aromatic group of the benzene series, Z and Z1 each represents the nonrnetallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and `X represents an anion and atleast one complex merocyanine dye selected `ethoXyethoxyethyl group, member selected from the group consisting of an` methyl group,` an ethyl group, and a phenyl 1 whereinV R2 represents a member selected from the group. consisting of ai methyl group, an` ethyl each` represents .a` member selected from the group-,consisting of, a` methyl', group, an` ethyl group, a, n-heptylgroup, a -methoxyethylf group. a carbethoxymethyl group; and a3-hydroxy-` R` represents@ a groupiv L. represents a methine group,` d representss a` positive integer of from l to 2, andwZz represents-the` `nonmetallic atoms necessary to: completen. heterocyclic` nucleus selected from the; group.- consisting of,` those of `the benzothiazole l seriesthose of the a-naphthothiazole series, those of the -,naphthothiazoleseries, those of the;

i benzoxadole series,` and those` of the quinoline series; l

6. A photographic; silver halide developing-out emulsion sensitized with a supersensitizing comblnation of at least one diaryloxythiacarbocyanine dye selectedA from those represented by the following general formula:

b==c-cn=cc-rligcrr1 0R. ORL X Y wherein Tt` and R1 each represents: ar mononuclear aromatic group of the benzene; series; Z` and Z1 each represents the lnonrnetallic` atoms; necessary' to complete a heterocyclic nucleus of the benzothiazole series, and at least one complex merocyanine dye selected from those represented by the following general formula:

wherein R2 represents a member selected from the group` consisting of a methyl group, an ethyl group, and a` -hydroxyethyl group, Rs and R4 each represents a member selected from the group consisting of a methyl group, an ethyl group, a n-heptyl` group, a /3-methoxyethyl group, aA carbethoxymethyl" group,4 and a ,S-hydroXy--ethoxy- -ethoxyethyl. group, R" represents a member selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group, d and n each represents a positive integer'of from 1 to 2, and Z2 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of' the a-naphthothiazole series.

7. A photographic silver halide developing-out emulsion sensitized with a supersensitizing combination of at least one diaryloxythiacarbocyanine'dye, selected from those represented by the following general formula:

wherein R and R1: each represents amononuclear aromatic group of the benzene series,` Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic` nucleusofz the benito--` thiazole series, and at least one complex merocy-z anine dye selected from those represented by the following general formula:

wherein R2, represents a member selected from the group consisting of a methyl group, an ethyl group, and a -hydroethyl group, R3 and R4 each represents a member selected from the group consisting of a methyl group, an ethyl group, a n-heptyl group, a -methoxyethyl group, a carbethoxymethyl group, and a -hydroXy--ethoxy- -ethoxyethyl group, R represents a member selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group, d and 11l each represents a positive integer of from 1 to 2, and Z2 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the -naphthothiazole series.

8. A photographic silver halide developing-out emulsion sensitized with a supersensitizing combination of at least one diaryloxythiacarbocyanine dye selected from those represented by the following general formula:

wherein R and R1 eachrepresents a mononuclear aromatic group of the benzene series, Z and Z1 each represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and at least one complex merocyanine dye selected from those represented by the following general formula:

wherein R2 represents a member selected from the group consisting of a methyl group, an ethyl group, and a -hydroethyl group, Ra and R4 each represents a member selected from the group consisting of a methyl group, an ethyl group, a n-heptyl group, a ,B-methoxyethyl group, a carbethoxymethyl group, Vand a -hydroXy-- ethoxy--ethoxyethyl group, R represents a member selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group. and a phenyl group, d and n each represents a positive integer of from 1 to 2, and Z2 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the benzoxazole series.

9. A photographic silver halide developing-out emulsion sensitized with a supersensitizing combination of at least one diaryloxythiacarbocyanineA dye selected from those represented by the following general formula.:

wherein R and R1 each represents a mononuclear aromatic group of the benzene series, Z and Z1 each represents the nonmetallic atoms necessary to complete a'heterocyclic nucleus of the benzothiazole series, and at least one complex merocyanine dye selected from those represented by the following general formula: l

wherein R2 represents a member selected from the group consisting of a methyl group, an ethyl group, and a -hydroethyl group, Ra and R4 each represents a member selected from the group consisting of a methyl group, an ethyl group, an n-heptyllgroup, a -methoxyethyl group, a carbethoxymethyl group, and a -hydroxy--ethoxy- -ethoxyethyl group, R represents a member selected from `thegroup consisting of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group, d and n each represents a positive integer of from 1 to 2, and Z2 represents the nonmetallic atoms necessary to complete a heterocyclic nucleus 'of the quinoline series, i

l0. A photographic silver halide developing-out f emulsion sensitized with a supersensit'zing combination of at least one diaryloxythiacarbocyanine dye selected from these represented by the following general formula:

wherein Rz represents a member selected from the group consisting of a methyl group, an ethyl group, and a Ic-hydroethyl group, R3 and 'R4 each represents a member selected from the group consisting of a methyl group, an ethyl group, an

n-heptyl group, a -methoxyethyl group, a carbethoxymethyl group, and a -hydroxy--ethoxy- -ethoxyethyl group, R represents a member selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, and a phenyl group, d and n each represents a positive L integer of from 1 to 2, and Z2 represents the nonmetallic atoms necessary to complete a:

heterocyclic nucleus of the benzothiazole series.

11. A photographic gelatino-silverhalide developing-out emulsion sensitized with a super-- (p-chlorosensitizing combination or 8,10-di phenoxy 3,3- dimethylthiacarbocyanine ptoluenesulfonate and 5-[ (1-ethyl2(1) --naphthothiazolylidene) -aethylethylidenel -3-,8- methoXyethyl-Z-(S--methoxyethyl -4- oxo-2- 12. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of 3,3dimethyl8,10 di(mtoloxy)thiacarbocyanine bromide and 5- [(3hydI`0Xye1hy1 2(3) -anaphthothiazolylidene) ethylidenel-S-- methoxyethyl -2-(3-,8-

methoXyethyl-fl-oxo -2-v thiono -5- thiazolidylidene) -4-thiazolidone.

13. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of 3,3'dimethyl8,10

di(mtoloxy)thiacarbocyanine bromide and 2- l 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION SENSITIZED WITH A SUPERSENSITIZING COMBINATION OF AT LEAST ONE DIARYLOXYTHIACARBOCYANINE DYE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 